Thiazole azo compounds



United States Patent 3,206,452 THIAZOLE AZO COMPOUNDS James M. Straleyand David J. Wallace, Kingsport, Tenn., assignors to Eastman KodakCompany, Rochester, N.Y., a corporation of New Jersey No Drawing. FiledJan. 7, 1963, Ser. No. 249,588 12 Claims. (Cl. 260-155) This inventionrelates to novel compounds containing a dicarboximido radical, and moreparticularly to azo compounds, such as azo dyestuffs, containing adicarboximido radical. Particular azo compounds containing this radicalinclude compounds obtained by coupling diazotized 2-aminothiazoles withdicarboximidoalkyl tetrahydroquinoline coupling components.

These particular azo compounds have the general formula R=a monocyclicZ-thiazolyl radical, that is, a radical having the formula in which V isa vinylene group, including substituted and unsubstituted vinylene,monoand di-substituted vinylene groups, such as --OH=CH-, -(|JH=CH and--(I3=C N O 2 C H3 430 CH3 as present in Z-aminothiazole and thesubstituted Z-aminothiazoles described in the examples below; the nitro,alkylsulfonyl, alkyl, and cyano substituted Z-aminothiazoles beingparticularly eflicacious for use in making the azo compounds;

R R and R each equal a hydrogen atom or a lower alkyl group,particularly methyl;

Y =the substituents in at least one of the 5-, 7- or 8- positions of thetetrahydroquinoline nucleus wherein Y is either a lower alkyl group,particularly methyl; a lower alkoxy group, particularly methoxy; or ahalogen atom, including a chlorine atom or a bromine atom;

n=a positive integer from 1 to 4;

R =an alkylene group straight or branch-chained, particularly loweralkylene, such as -(CH wherein 11' is a positive integer from 1 to 4,

Z=a dicarboximido radical such as phthalimido, succinimido, maleimido,citraconimido, etc., as indicated in the examples below, derived iromthe corresponding anhydride.

The Z-aminothiazoles which are diazotized and coupled with the mentionedcoupling components are, for example, Z-aminothiazole,2-amino-5-nitrothiazole, '2-amino-5-alkylsulfonylthiazoles and otherZ-aminothiazoles disclosed in the examples hereinafter.

3,206,452 Patented Sept. 14, 1965 The dicarboximidoalkyltetrahydroquinoline coupling components of the invention which arecoupled with the diazotized Z-aminothiazoles, have the following generalformula R1 /H 4@ Hi Ya 1 wherein R R R R Y, n and Z have the samemeaning as given above.

The dicarboximido radical Z of the azo compounds and coupling componentsof Formulas I and 11 above, has the following general formula Thedicarboximidoalkyl tetrahydroquinoline coupling components are obtainedas described in the followinig typical reaction, by the condensation ofa dicarboxylic acid anhydride with an N-aminoalkyltetrahydroquinoline CO-GHZ (BHIOHPN COCH Representative 5- and 6-membered cyclicdicarboximidoalkyl tetrahydroquinoline couplers referred to in theexamples below, useful for preparing the azo compounds are:

N-B-succinimidoethyl l,2,3,4-tetrahydroquinolineN-succinimidomethyl-l,2,3,4-tetrahydroquinolineN-fl-succinimidoethyl-2,7-dimethyl-l,2,3,4-tetrahydroquinoline 3N-fl-phthalim-idoethyl-l,2,3,4-tetrahydroquinolineN-fl-succinimidoethyl-2,2,4,-tetramethyl-1,2,3,4-tetrahydroquinolineN-ot-succinirnidopropyl-Z,7-dimethyl-1,2,3 ,4-tetrahydro N -B-succinimidoethyl-2,2,4-tri-methyl-1,-2,3,4-tetrahydroquinolineN-fl-succinimidoethyl-Z-methyl-l,2,3,4-tetrahydroquinolineN-B-succinimidoethyl-Z-isop-ropyl-7-methoxy-1,2,3,4-tetrahydroquinolineThe azo compounds can be used for dyeing textile materials includingsynthetic polymer fibers, yarns and fabrics giving fast blue to violetshades when applied by conventional dyeing methods to cellulose esterand polyester fibers. The azo compounds have moderate afiinity forpolyamide fibers and possess the valuable property of staining wool lessthan do previous thiazole azo dyes. When the azo compounds are used fordyeing suchhydrophobic materials, they should be free ofwater-solubilizing groups such as sulfo and carboxyl groups. In general,the dyes have good fastness, for example, to light, washing, gas(atmospheric fumes) and sublimation. The dyes are useful in applicationand discharge printing.

The following examples will serve to illustrate the preparation ofrepresentative intermediates and azo compounds of our invention.

EXAMPLE 1 N -fl-succinimidethyl-2,7-dim ethyl-1 ,2,3,4-tetrahydr0-quinoline 20.4 g. (0.1 m.) N-2-aminoethyl-Z,7-dimethyl-1,2,3,4-tetrahydroquinoline, 10.0 g. (0.1 In.) succinic anhydride, and 1 g.sulfanilic acid are heated at 140150 C. for 1 hour. The reaction mixtureis poured into 300 ml. of ethanol and this suspension is heated tosolution. On cooling, a solid results. Yield-48.3 g., M.P. 142-145 C.Recrystallized from ethanol the products melts at 146- 147 C. The courseof the reaction of this example is provided in the above description.

EXAMPLE 2 N-fl-succinimidoethyl-I,2,3,4-tetrahydroquinoline 17.6 g. (0.1m.) N-2-aminoethyl-1,2,3,4-tetrahydroquinoline and 10.0 g. (0.1 m.)succinic anhydride are heated together at 135-140 C. for 1 hour. Thismixture is poured while hot into 200 m1. of ethanol. On cooling, theproduct crystallizes. Yield, 14.8 g., MP. 111- 113 C.

' The other dicarboximidoalkyl tetrahydroquinoline couplers can beprepared by the method of Examples 1 and 2 by reaction of theappropriate anhydride with the appropriateN-aminoalkyltetrahydroquinoline.

EXAMPLE 3 Preparation of azo compound (a) Diaz0tizati0n.-l.45 g. (0.01m.) 2-amino-5-nitrothiazole is stirred in 30 ml. of water, and 16 m1.conc. sulfuric acid is added, causing immediate solution. The solutionis cooled to l0 C. and a solution of 0.72 g. (0.0104 In.) sodium nitritein 8 ml. conc. sulfuric acid is added portionwise below C. The mixtureis stirred 2 hours at 10 to -5 C.

(b) C0upling.2.86 g. (0.01 m.)N-fl-succinimidoethyl-2,7-dimethyl-1,2,3,4-tetrahydroquinoline isdissolved in 50 ml. of '15 aqueous sulfuric acid, and the solution coolsin an ice-bath. The diazonium solution from (a) above is added, thereaction mixture allowed to stand 2 hours in the ice-bath, then drownedwith water. The dye is filtered otf, washed with water, and dried. Theproduct dyes cellulose acetate desirable blue shades with fonylthiazole.

4. good fastness properties. The azo compound has the formula ti 1 OgNCCN=N- EXAMPLE 4 The procedure of Example 3 is carried out except thatthe coupler used is 3.06 g. of N-[i-phthalimidoethyl-1,2,3,4-tetrahydroquinoline. The yield is 3.5 g. of product whichimparts bright blue shades to cellulose acetate fabric.

EXAMPLE 5 The procedure of Example 3 is carried out except that thediazo component is 1.68 g. of 2-amino-4-trifiuoromethylthiazole. Theyield is 3.25 g. of product which dyes cellulose acetate and polyesterfabrics in violet shades.

EXAMPLE 6 The procedure of Example 3 is carried out except that thediazo component used is 1.26 g. of 2-an1ino-4- methylthiazole. Theproduct dyes cellulose acetate fabrics in violet shades.

EXAMPLE 7 The procedure of Example 3 is carried out except that thediazo component used is 2.21 g. 2-amino-5-butylsul- The product dyescellulose esters and polyester fibers in blue shades.

EXAMPLE 8 The procedure of Example 3 is carried out except thatmethyl-1,2,3,4-tetrahydroquinoline. The product dyes cellulose acetateand polyester fabrics in bright blue shades.

EXAMPLE 9 The procedure of Example 3 is carried out except that thecoupler used is 3 g. of N-a-succinimidopropyl-2,7-dimethyl-1,2,3,4-tetrahydroquinoline. The product produces bright blueshades on cellulose acetate and polyester fibers.

EXAMPLE 10 The procedure of Example 3 is carried out except that thecoupler used is 3 g. of N-B-succinimidoethyl-2,2,4.trimethyl-l,2,3,4-tetrahydroquinoline. The product dyes celluloseacetate fibers blue shades.

The azo compounds described in the following table are prepared inthernanner of the above examples using the indicated diazotized2-aminotl1iazoles and dicarboxim-idoalkyltetrahydroquinoline couplers. YR R and Z refer to the general formulas above wherein R and R arehydrogen atoms. Thus, the azo compound of Example 3, included in thetable for illustration, is prepared from Z-amino-S-nitrothiazole andN-B-succinimidoethyl-2,7-dimethyl-1,2,3,4-tetrahydroquinoline asdescribed in detail in Example 3 above. In the table, the color of thedyeings Iefersto the 'color obtainable by dyeing a cellulose acetatefabricwith the azo compound.

Dicarboximidoalkyltetrahydroquinoline Coupler Example z-AminothiazoleYn-l R4 R; Z Color of No, Diazotized Dyelngs 3 5-NO2 7-CHa CH2CHz-Srmm'nimidn B1 4 5-N02 H CH2OH a 5-NO' 7-C CHzCHa Do, a 5-NO'1 mmCHzOHz-- Do. 7 5-N02 7-CHa -CHzCHr- Citraeonimido DQ 8'. 5-N0a 7-OH8CH2CH2 Hexahydrophthalimido Do. q 5.N0-, 7-611 GH2CH2Tetrahydrophthalimido Do. 10 6-N01 7-CHa --CH2GH2 3-nitrophthallmido Do.11 5-N0z 7-0113 HzCHz- Chloaotetrahydrophtha Do.

m1 0. CilHs 12 eNoi 7-OHa -CHCH2CHz- 2-CH: Succinlmido Do. 13 5- 0z7-CHa CH2CHz 2-isopropyl do acrri do Do. (in D0. do Do. do Do. Do.4-NHCOOH3 "an Violet Norm dfi Blue. 4-0113, E-COCH: CH2CH2 2-0 doViolet. 5-CN -CHzCHz- 2-CT' do Blue,

CHzOHz-- aorta dn Violet. -OH2CH2. 2cm do Do. OHCH3 aorrt do Do. CH2Z-CH; Glutarimido Blue.

The azo compounds of the invention may be used for What we claim is:dyeing hydrophobic fibers such as linear polyester, cel- 1. A20compounds having the general formula lulose ester, acrylic, polyamide,etc., fibers in the manner described in U.S. Patents 2,880,050,2,757,064, 2,782,187 R H and 3,043,827. RN=N Since the azo compounds ofthe invention are water- H insoluble, they can be applied from aqueousdispersions Yr1 in the manner of the so-called dispersed dyes. How- R2ever, coloration can also be effected, for example, by incorporating theazo compounds into the spinning dope RFZ and spinning the fiber asusual. The azo compounds of our invention have varying utility as dyes.The degree 40 wherein of utility varies, for example, depending upon themate- R=a monocyclic-Z-thiazolyl radical, rial being dyed and theformula of the azo compound. R R and R each=a member of the classconsisting Thus, for example, all the dyes will not have the same of ahydrogen atom and a lower alkyl group, degree of utility for the samematerial. R =l0wer alkylene,

Cellulose esters which can be dyed with the azo com- =a m mber of theclass consisting of a lower alkyl pounds include cellulose aliphaticcarhoxylic acid esters P Y p, chlorine and bromine, having 2 to 4 carbonatoms in the acid groups thereof, PQ P i f 1 t0 and by which We mean toinclude, for example, both partially lmldo radical hydrolyzed andunhydrolyzed cellulose acetate, cellulose AZO Compounds according to01mm 1 Whefelll 4 propionate and cellulose acetatcbutyrate. 13 aethylene g p- 3. A20 compounds according to claim 1 wherein R is a5-nitro-2-thiazolyl radical.

4. A20 compounds according to claim 1 wherein R=a monocyclicZ-th-iazolyl radical, R =a lower alkylene group, Z=a succinimido radicaland at least one of R R R and Y is a methyl group and the remainderPolymeric linear polyester materials of the terephthalate type areillustrative of the linear aromatic polyester textile materials that canbe dyed with the new azo compounds of our invention. The terephthalatefibers sold under the trademarks Kodel, Dacron and Terylcue, forexample, in the form of filaments, yarn and fabric, for example, areillustrative of the polyester textile are hydrogen atoms materials thatcan be dyed. Kodel polyester fibers are more particularly described inU.S. Patent 2,901,446. i=i in sd dgy d l i g 2 flii a z dly l ad iilwherem Dacron and Terylene polyester fibers are described, for -R CH CHexample, in U.S. Patent 2,465,319. The polymeric linear Z=a succinimidoradical and at least one of R R polyester materials disclosed in U.S.Patents 2,945,010, R and Y,, is a methyl group and the remainde r"2,957,745 and 2,989,363, for example, can be dyed. The are hydrogenatoms. linear aromatic polyester materials specifically named AZOCompounds according to Claim 1 ere n have a melting point of at least200 C. monocyclic z-thiazolyl radical,

Nylon, in fiber yarn and fabric form, is representative lower alkylenep, of polyamides which can be dyed with the azo com- Zza Phthaljmidoradical and at least one Of 1 2 pounds R and Y is a methyl group and theremainder The invention has been described in considerable detail 7 ii;gfgggfi gg sg t 1 1 h r mg 0 c mm W erein with particular reference tocertain preferred embodi- 2 merits thereof, but it will he understoodthat variations R:- 1 1 l- I flmmlyl radical and modifications can beeffected within the spirit and 2 y Z=a hthal scope oi the invention asdescribed herelnabove, and as R3 5 y 2 1 2 1 at leasg i of R13 defined111 the appended claims. are hydrogeri atoms y g oup an t e TemamderUNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION.

Patent No. 3 ,206 ,452 September 14, 1965 James M. Straley et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 7, the formula in claim 8 should appear as shown below instead ofas in the patent:

column 8, the formula in claim ll should appear as shown below insteadof as in the patent:

Signed and sealed this 10th day of May 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. AZO COMPOUNDS HAVING THE GENERAL FORMULA